EP1964969B1 - Coating compositions - Google Patents

Coating compositions Download PDF

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Publication number
EP1964969B1
EP1964969B1 EP08152014.0A EP08152014A EP1964969B1 EP 1964969 B1 EP1964969 B1 EP 1964969B1 EP 08152014 A EP08152014 A EP 08152014A EP 1964969 B1 EP1964969 B1 EP 1964969B1
Authority
EP
European Patent Office
Prior art keywords
composition
starch
paper
cold water
coating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP08152014.0A
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German (de)
English (en)
French (fr)
Other versions
EP1964969A1 (en
Inventor
Marc Charles Florent Berckmans
Detlev Glittenberg
Rudy Roux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cargill Inc
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Cargill Inc
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Publication date
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Application filed by Cargill Inc filed Critical Cargill Inc
Priority to EP08152014.0A priority Critical patent/EP1964969B1/en
Publication of EP1964969A1 publication Critical patent/EP1964969A1/en
Application granted granted Critical
Publication of EP1964969B1 publication Critical patent/EP1964969B1/en
Revoked legal-status Critical Current
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the present invention relates to coating compositions and, in particular, to paper coating compositions containing specific starchy materials.
  • Coating compositions are used on a number of substrates including, amongst others, metals, plastics, textiles and paper. They help to protect and enhance the feel and appearance of the surfaces to which they are applied. They may also improve other characteristics such as printability, water resistance, reflectivity or strength.
  • a coating composition will depend on its desired end-use.
  • a paper coating composition also known as a "coating colour”
  • binders and thickeners.
  • Thickeners in particular, have to be chosen very carefully as they are responsible for determining the coating composition's rheological properties (both at high and low shear) and will contribute to it having an appropriate stability (e.g. during storage or at the high temperatures required for drying).
  • a number of starch products have been developed. The aim of these developments has been the production of a cheap, highly stable, highly viscous, cold water soluble starch.
  • US2849326 relates to a composition and method of preparation of pigments coating containing high solids content for paper and polymers derived from starch.
  • GB602223 relates to the manufacturing of cold-water soluble and cold-water swelling starches and their use in sand cores, as odour binders and for coating and sizing of paper, textiles and the like.
  • a coating composition comprising a cold water soluble starch and one or more binders, thickeners and/or pigments characterized in that said cold water soluble starch is derived from a starch selected from the group consisting of wheat starch, corn starch and mixtures thereof, and has a DE of less than 5 and has :
  • a coating composition comprising a cold water soluble starch and one or more binders, thickeners and/or pigments characterized in that said cold water soluble starch is derived from a starch selected from the group consisting of wheat starch, corn starch and mixtures thereof, and has a DE of less than 5 and has :
  • the CWSS is derived from a starch selected from the group consisting of: corn starch, wheat starch, and mixtures thereof.
  • modified starch refers to a starch whose structure has been altered by chemical, enzymatic or heat treatment.
  • the starch substrate may be selected from esterified, etherified, cross-linked, oxidised or acid modified starches or mixtures of two or more thereof.
  • the CWSS of the invention is not be strongly degraded; in other words, it has a dextrose equivalence (DE) value of less than 5, more preferably of less than 4, more preferably of less than 3, more preferably of less than 2 (wherein DE is measured using the Schoorl Method).
  • DE dextrose equivalence
  • the CWSS of the present invention Before solubilisation, the CWSS of the present invention will have a granular structure. Native starch granules exist in many shapes and sizes. Under the influence of heat and in the presence of water, these granules swell and, eventually, disperse leading to a colloidal solution. Thus, the CWSS of the present invention will preferably have, before solubilisation, a granular structure similar to that of its corresponding native starch.
  • the CWSS of the present invention has a number average molecular weight (Mn) of 3 500 to 20 000 Daltons. Preferably, it will be between 5 000 and 15 000 Daltons.
  • the CWSS has a cold water solubility (SI) of 30-90%, preferably of 45-90%, more preferably of 50-80%.
  • Cold water solubility is measured according to Method 1 set out below and generally refers to the proportion of starch granules that are able to swell in cold water (i.e. at neutral pH and at room temperature), forming a viscous, colloidal dispersion.
  • cold water soluble starches may also be referred to as "cold water swellable" starches.
  • the CWSS of the present invention will fully disperse and solubilise when used in the preparation of a typical industrial coating composition, i.e. at a pH of 8-10 and at a temperature of 30-50°C.
  • it should have a solubility (S2) at pH 10 / 35°C (see Method 2) which is at least 10% greater than (SI).
  • S2 solubility
  • S2 solubility
  • S2 solubility of at least 70%.
  • Coating compositions are typically used to enhance the feel, appearance and/or functionality of a substrate.
  • the term "coating composition” will refer to any aqueous solution or dispersion suitable for such a use, and to dry mixes used in their preparation. In the case of an aqueous solution or dispersion, it should ideally contain 30-75% dry substance by weight.
  • the coating composition of the present invention will be a paper coating composition (also know as a "coating color"). It will advantageously comprise at least 50% dry substance by weight, more preferably 50-80%.
  • the composition will advantageously have a pH of 7 to 12. Preferably, the pH will be from 8 to 10.
  • it will further contain one or more pigments. It may also contain one or more binders, one or more thickeners and one or more additives.
  • Suitable pigments include: clays such as kaolin but also structured and calcined clays, hydrated aluminum silicates, bentonite, natural and synthetic calcium carbonate, calcium sulphate (gypsum), silicas, precipitated silicas, titanium dioxide, alumina, aluminium trihydrate, plastic (polystyrene) pigments, satin white, talc, barium sulphate, zinc oxide and mixtures of two or more thereof.
  • clays such as kaolin but also structured and calcined clays, hydrated aluminum silicates, bentonite, natural and synthetic calcium carbonate, calcium sulphate (gypsum), silicas, precipitated silicas, titanium dioxide, alumina, aluminium trihydrate, plastic (polystyrene) pigments, satin white, talc, barium sulphate, zinc oxide and mixtures of two or more thereof.
  • clays such as kaolin but also structured and calcined clays, hydrated aluminum silicates, bentonit
  • the composition of the invention may comprise: one or more binders. They can indeed be replaced, either in whole or in part, by the CWSS of the present invention.
  • the binder can be selected - by way of example only - from carbohydrate- based binders including starch-based binders (such as oxidised or esterified starch) and cellulose binders (such as CMC and hydroxyethyl cellulose), protein binders (such as casein, gelatine, soy protein and animal glues) and synthetic binders, especially latex binders (such as styrene butadiene, styrene acrylate, vinyl polymer based latexes and polyvinyl alcohol) together with mixtures of two or more thereof.
  • starch-based binders such as oxidised or esterified starch
  • cellulose binders such as CMC and hydroxyethyl cellulose
  • protein binders such as casein, gelatine, soy protein and animal glues
  • composition of the invention may comprise additional thickeners. Again, they can be replaced, in whole or in part, by the CWSS of the present invention. If further thickeners are used, they should not account for more than 50% of total thickener content on a dry weight basis.
  • suitable thickeners include cellulose ethers (such as CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethyl cellulose and methyl cellulose), alginates (such as sodium alginate), xanthan, carrageenans, galactomannans (such as guar), native or modified starches (such as roll-dried starch), synthetic polymers (such as polyacrylates) and mixtures of two or more thereof.
  • additives may include: surfactants (e.g. cationic surfactants, anionic surfactants, non-ionic surfactants, amphoteric surfactants and fluorinated surfactants), hardeners (e.g. active halogen compounds, vinylsulfone compounds, epoxy compounds, etc.), dispersing agents (e.g. polyacrylates, polyphosphates, polycarboxylates, etc.), flowability improvers, lubricants (e.g. calcium, ammonium and zinc stearate, wax or wax emulsions, alkyl ketene dimer, glycols, etc.), antifoamers (e.g.
  • surfactants e.g. cationic surfactants, anionic surfactants, non-ionic surfactants, amphoteric surfactants and fluorinated surfactants
  • hardeners e.g. active halogen compounds, vinylsulfone compounds, epoxy compounds, etc.
  • dispersing agents e.g. poly
  • octyl alcohol silicone-based antifoamers, etc.
  • releasing agents foaming agents, penetrants, optical brighteners (e.g. fluorescent whiteners), preservatives (e.g. benzisothiazolone and isothiazolone compounds), biocides (e.g. metaborate, thiocyanate, sodium benzonate, etc.), yellowing inhibitors (e.g. sodium hydroxymethyl sulfonate, sodium p-toluenesulfonate, etc.), ultraviolet absorbers (e.g. benzotriazole compounds having a hydroxy-dialkylphenyl group at the 2 position), antioxidants (e.g.
  • sterically hindered phenol compounds insolubilisers, antistatic agents, pH regulators (e.g. sodium hydroxide, sulfuric acid, hydrochloric acid, etc.), water-resisting agents (e.g. ketone resin, anionic latex, glyoxal, etc.), wet and/or dry strengthening agents (e.g. glyoxal based resins, oxidised polyethylenes, melamine resins, urea formaldehyde, etc.), cross-linking agents, gloss-ink holdout additives.
  • pH regulators e.g. sodium hydroxide, sulfuric acid, hydrochloric acid, etc.
  • water-resisting agents e.g. ketone resin, anionic latex, glyoxal, etc.
  • wet and/or dry strengthening agents e.g. glyoxal based resins, oxidised polyethylenes, melamine resins, urea formaldehyde, etc.
  • Reference Precoat Precoat of the invention Coarse Ground Calcium Carbonate (parts) 100 100 Styrene Butadiene Latex (parts) 6.5 5.5 Chrono HV 117 1 (parts) - 3 C*FilmTCF 07311 (parts) 7 5 Fluorescence Whitening Agent (parts) 0.5 0.5 Polyacrylate Thickener (parts) 0.3 0.1 Dry Solids (%) 66.1 68.2 CWSS in accordance with the invention Standard Middlecoat Standard Topcoat Ground Calcium Carbonate (parts) 100 60 Kaolin clay (parts) - 40 Middlecoat latex (parts) 5 - Topcoat Latex (parts) - 6.5 C*FilmTCF 07311 (parts) 7 - CMC (parts) 0.3 0.35 Fluorescence Whitening Agent (parts) 0.1 0.2 PVOH (parts) - 1 Ca-stearate (parts) - 0.25 Dry Solids (%) 69 68.5
  • Reference precoat the jet cooked (130°C) starch paste was added hot (> 80°C) into the pigments prior to the addition of latex and additives.
  • Reference topcoat the jet cooked (130°C) starch paste was added hot (> 80°C) into the pigments prior to the addition of latex 1 and latex 2. Afterwards, the PVOH, FWA and thickener are added to the suspension.
  • Topcoat of the invention Chrono HV 170 was mixed under high-shear conditions for 8 minutes in the pigment slurry/latex blend prior to the addition of PVOH and FWA.
  • Coating 126 g/m 2 standard pre and middle coated paper used as base. 10.5 g/m 2 per side top-coat weight (stiff blade 0.508 mm, 1400 m/min). Paper was calendered at 200m/min, 80°C and at a nip pressure of 180kN/m.
  • Precoat of the invention Chrono HV 117 was mixed under high-shear conditions for 8 minutes in the pigment slurry/C*Film blend prior to the addition of latex, FWA and synthetic thickener.
  • Coating 84 g/m 2 base paper with 10 g/m 2 per side pre-coat (MSP, 1000 m/min), followed by standard middle and top coats (free jet applicator, 1400 m/min). Paper was calendered at 200m/min, 80°C and at a nip pressure of 180kN/m.
  • Example 2 Top coating of fine paper with free jet applicator
  • Reference topcoat the jet cooked (130°C) starch paste was added hot (> 80°C) into the pigments prior to the addition of latex 1 and latex 2. Afterwards, the PVOH, FWA and thickener are added to the suspension.
  • Topcoat of the invention Chrono HV 170 was mixed under high-shear conditions for 8 minutes in the pigment slurry/latex blend prior to the addition of PVOH and FWA.
  • Coating 126 g/m 2 standard pre and middle coated paper used as base. 10.5 g/m 2 per side top-coat weight (stiff blade 0.508 mm, 1400 m/min). Paper was calendered at 200m/min, 80°C and at a nip pressure of 180kN/m.
  • Both control levers - "Pressure” and “Cylinder” - have to be in the "off' position (downwards). At least three filter papers should be weighed and the figure logged (weight 1). The filters have to be placed on the rubberised plate and the Millipore filter is then placed on the filter papers with the shiny side up. Then the cylinder is placed on the plate with the ceiling upward. The whole composition is put on the metal plate and risen up by switching the "Cylinder" lever.
  • the sample is tempered to 30°C and 10 mL of the coating colour is filled into the cylinder with a syringe.
  • the rubber should be free from coating colour to avoid leakage.
  • the exact ink amount on the paper surface should be determined in [mg] or [g] by using an analytical balance (+/- 0.1 mg or +/- 0.0001 g exactly).
  • the applied ink amount can be calculated by weighing the inked printing disc before and after printing.
  • 3 stripes should be printed on each side.
  • the printing gloss should be determined either with Gardner or Lehmann glossmeter (10 measurements on each stripe).
  • the printing gloss should be calculated to a coat weight of 1.2 g/m 2 for coated papers and 1.5 g/m 2 for uncoated papers by using regression analysis (either with calculator or Nomo-diagram).
  • the dry-pick test is used to determine the surface strength of the coated and uncoated papers and boards. Picking is a surface damage caused by the adhesion force of the printing ink during the printing process. The adhesion force on the surface becomes higher at higher printing speeds and with inks exerting a higher tack. The printing pressure and ink layer thickness also influence the picking.
  • the printing disc is inked according to the IGT- procedure under above-mentioned conditions. At least 3 stripes of each sample and side are printed. Only the clear visible beginning of the picking is noticed. The pick result is calculated by means of the IGT-Nomogram. Viscosities of test inks for IGT dry pick: Ink type: Viscosity at 23°C Pa.s H-oil 110 N-oil 52 L-oil 17,5 Lorilleux 3802 16 Lorilleux 3803 26 Lorilleux 3804 35 Lorilleux 3805 40 Lorilleux 3806 50
  • Mottling is the unevenness of the print of the paper or board due to irregular ink setting. It occurs on the multiple-colour offset machine by different film splitting on the successive rubber blankets and usually after first and second print. The mottling test simulates the printing process on the laboratory printing machine under constant conditions and evaluated visually after test printing.
  • Test stripe should be printed under the above-mentioned conditions. Is after printing three counter prints must be done with the un-inked disc. The printed stripe is evaluated with an image analysing system via scanner.
  • the image of the paper strip is measured via a scanner in seven different resolution stages. The higher the calculated value, the stronger the mottling pronounced in this stage.
  • the exact ink amount on the paper surface should be determined in [mg] or [g] by using an analytical balance (+/- 0.1 mg or +/- 0.0001 g exactly).
  • the applied ink amount can be calculated by weighing the inked printing disc before and after printing.
  • each strip is printed in machine direction. After conditioning the printed papers (23°C/50%) for 24 hours, each strip is laid separately in an oven for 15 seconds at 120 °C. With the printing side outside, the paper is slightly pre-folded and fixed on the educabau rubber matrix.

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  • Paper (AREA)
  • Paints Or Removers (AREA)
EP08152014.0A 2007-02-27 2008-02-27 Coating compositions Revoked EP1964969B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08152014.0A EP1964969B1 (en) 2007-02-27 2008-02-27 Coating compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07103158 2007-02-27
EP08152014.0A EP1964969B1 (en) 2007-02-27 2008-02-27 Coating compositions

Publications (2)

Publication Number Publication Date
EP1964969A1 EP1964969A1 (en) 2008-09-03
EP1964969B1 true EP1964969B1 (en) 2018-07-11

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ID=38180397

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EP08152014.0A Revoked EP1964969B1 (en) 2007-02-27 2008-02-27 Coating compositions

Country Status (8)

Country Link
US (1) US20080206571A1 (pt)
EP (1) EP1964969B1 (pt)
JP (1) JP5570820B2 (pt)
CN (1) CN101255667B (pt)
BR (1) BRPI0807664A2 (pt)
CA (1) CA2679073A1 (pt)
ES (1) ES2683053T3 (pt)
WO (1) WO2008104574A1 (pt)

Cited By (1)

* Cited by examiner, † Cited by third party
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US11441017B2 (en) 2017-05-16 2022-09-13 Cargill, Incorporated Article of manufacture containing a starch-converted material

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US20080206571A1 (en) 2008-08-28
EP1964969A1 (en) 2008-09-03
CN101255667B (zh) 2013-07-31
JP2010519429A (ja) 2010-06-03
WO2008104574A1 (en) 2008-09-04
CA2679073A1 (en) 2008-09-04
ES2683053T3 (es) 2018-09-24
BRPI0807664A2 (pt) 2014-05-20
JP5570820B2 (ja) 2014-08-13
CN101255667A (zh) 2008-09-03

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